Rare earth permanent magnets and their preparation

ABSTRACT

A sintered magnet body (R a T 1   b M c B d ) coated with a powder mixture of an intermetallic compound (R 1   i M 1   j , R 1   x T 2   y M 1   z , R 1   i M 1   j H k ), alloy (M 1   d M 2   e ) or metal (M 1 ) powder and a rare earth (R 2 ) oxide is diffusion treated. The R 2  oxide is partially reduced during the diffusion treatment, so a significant amount of R 2  can be introduced near interfaces of primary phase grains within the magnet through the passages in the form of grain boundaries. The coercive force is increased while minimizing a decline of remanence.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a Divisional of U.S. application Ser. No. 15/454,433, filed on Mar. 9, 2017, and wherein U.S. application Ser. No. 15/454,433 is a Divisional of U.S. patent application Ser. No. 13/461,043 filed on May 1, 2012, which is a non-provisional application which claims priority under 35 U.S.C. § 119(a) on Japanese Patent Application Nos. 2011-102787 and 2011-102789 filed in Japan on May 2, 2011 and May 2, 2011, respectively, the entire contents of which are hereby incorporated by reference.

TECHNICAL FIELD

This invention relates to an R—Fe—B permanent magnet having an enhanced coercive force with a minimal decline of remanence, and a method for preparing the same by coating a sintered magnet body with a mixture of an intermetallic compound, alloy or metal powder and a rare earth oxide and heat treating the coated body for diffusion.

BACKGROUND ART

By virtue of excellent magnetic properties, Nd—Fe—B permanent magnets find an ever increasing range of application. The recent challenge to the environmental problem has expanded the application range of these magnets from household electric appliances to industrial equipment, electric automobiles and wind power generators. It is required to further improve the performance of Nd—Fe—B magnets.

Indexes for the performance of magnets include remanence (or residual magnetic flux density) and coercive force. An increase in the remanence of Nd—Fe—B sintered magnets can be achieved by increasing the volume factor of Nd₂Fe₁₄B compound and improving the crystal orientation. To this end, a number of modifications have been made. For increasing coercive force, there are known different approaches including grain refinement, the use of alloy compositions with greater Nd contents, and the addition of coercivity enhancing elements such as Al and Ga. The currently most common approach is to use alloy compositions having Dy or Tb substituted for part of Nd.

It is believed that the coercivity creating mechanism of Nd—Fe—B magnets is the nucleation type wherein nucleation of reverse magnetic domains at grain boundaries governs a coercive force. In general, a disorder of crystalline structure occurs at the grain boundary or interface. If a disorder of crystalline structure extends several nanometers in a depth direction near the interface of grains of Nd₂Fe₁₄B compound which is the primary phase of the magnet, then it incurs a lowering of magnetocrystalline anisotropy and facilitates formation of reverse magnetic domains, reducing a coercive force (see Non-Patent Document 1). Substituting Dy or Tb for some Nd in the Nd₂Fe₁₄B compound increases the anisotropic magnetic field of the compound phase so that the coercive force is increased. When Dy or Tb is added in an ordinary way, however, a loss of remanence is unavoidable because Dy or Tb substitution occurs not only near the interface of the primary phase, but even in the interior of the primary phase. Another problem arises in that amounts of expensive Tb and Dy must be used.

Besides, a number of attempts have been made for increasing the coercive force of Nd—Fe—B magnets. One exemplary attempt is a two-alloy method of preparing an Nd—Fe—B magnet by mixing two powdered alloys of different composition and sintering the mixture. Specifically, a powder of alloy A consisting of R₂Fe₁₄B primary phase wherein R is mainly Nd and Pr, and a powder of alloy B containing various additive elements including Dy, Tb, Ho, Er, Al, Ti, V, and Mo, typically Dy and Tb are mixed together. This is followed by fine pulverization, molding in a magnetic field, sintering, and aging treatment whereby the Nd—Fe—B magnet is prepared. The sintered magnet thus obtained produces a high coercive force while minimizing a decline of remanence because Dy and Tb are absent at the center of R₂Fe₁₄B compound primary phase grains and instead, the additive elements like Dy and Tb are localized near grain boundaries (see Patent Documents 1 and 2). In this method, however, Dy and Tb diffuse into the interior of primary phase grains during the sintering so that the layer where Dy and Tb are localized near grain boundaries has a thickness equal to or more than about 1 micrometer, which is substantially greater than the depth where nucleation of reverse magnetic domains occurs. The results are still not fully satisfactory.

Recently, there have been developed several processes of diffusing certain elements from the surface to the interior of a R—Fe—B sintered body for improving magnet properties. In one exemplary process, a rare earth metal such as Yb, Dy, Pr or Tb, or Al or Ta is deposited on the surface of Nd—Fe—B magnet using an evaporation or sputtering technique, followed by heat treatment, as described in Patent Documents 3 to 5 and Non-Patent Documents 2 and 3. Another exemplary process involves applying a powder of rare earth inorganic compound such as fluoride or oxide onto the surface of a sintered body and heat treatment as described in Patent Document 6. With these processes, the elements (e.g., Dy and Tb) disposed on the sintered body surface pass through grain boundaries in the sintered body structure and diffuse into the interior of the sintered body during the heat treatment. As a consequence, Dy and Tb can be enriched in a very high concentration at grain boundaries or near grain boundaries within sintered body primary phase grains. As compared with the two-alloy method described previously, these processes produce an ideal morphology. Since the magnet properties reflect the morphology, a minimized decline of remanence and an increase of coercive force are accomplished. However, the processes utilizing evaporation or sputtering have many problems associated with units and steps when practiced on a mass scale and suffer from poor productivity.

Besides the foregoing methods, Patent Document 6 discloses a method comprising coating a surface of a sintered body with a powdered rare earth inorganic compound such as fluoride or oxide and heat treatment, and Patent Document 8 discloses a method comprising mixing an Al, Cu or Zn powder with a fluoride, coating a magnet with the mixture, and heat treatment. These methods are characterized by a very simple coating step and a high productivity. Specifically, since the coating step is carried out by dispersing a non-metallic inorganic compound powder in water, immersing a magnet in the dispersion and drying, the step is simple as compared with sputtering and evaporation. Even when a heat treatment furnace is packed with a large number of magnet pieces, the magnet pieces are not fused together during heat treatment. This leads to a high productivity. However, since Dy or Tb diffuses through substitution reaction between the powder and the magnet component, it is difficult to introduce a substantial amount of Dy or Tb into the magnet.

Further Patent Document 7 discloses coating of a magnet body with a mixture of an oxide or fluoride of Dy or Tb and calcium or calcium hydride powder, followed by heat treatment. During the heat treatment, once Dy or Tb is reduced utilizing calcium reducing reaction, Dy or Tb is diffused. The method is advantageous for introducing a substantial amount of Dy or Tb into the magnet, but less productive because the calcium or calcium hydride powder needs careful handling.

Patent Documents 9 to 13 disclose coating of the sintered body surface with a metal alloy instead of a rare earth inorganic compound powder such as fluoride or oxide, followed by heat treatment. The method of coating with only metal alloy has the drawback that it is difficult to coat the metal alloy onto the magnet surface in a large and uniform coating weight. In Patent Documents 14 and 15, a metal powder containing Dy and/or Tb is diffused into the mother alloy. The oxygen concentration of the mother alloy is restricted below 0.5% by weight, and the rare earth-containing metal powder is closely contacted with the mother alloy by a barrel painting technique of oscillating impact media within a barrel for agitation. Diffusion takes place under these conditions. However, this method requires many steps as compared with the method of coating a mother alloy magnet with a dispersion of a powder mixture of an intermetallic compound and a rare earth oxide in a solvent. The method is time consuming and is not industrially useful.

CITATION LIST

-   Patent Document 1: JP 1820677 -   Patent Document 2: JP 3143156 -   Patent Document 3: JP-A 2004-296973 -   Patent Document 4: JP 3897724 -   Patent Document 5: JP-A 2005-11973 -   Patent Document 6: JP 4450239 -   Patent Document 7: JP 4548673 -   Patent Document 8: JP-A 2007-287874 -   Patent Document 9: JP 4656323 -   Patent Document 10: JP 4482769 -   Patent Document 11: JP-A 2008-263179 -   Patent Document 12: JP-A 2009-289994 -   Patent Document 13: JP-A 2010-238712 -   Patent Document 14: WO 2008/032426 -   Patent Document 15: WO 2008/139690 -   Non-Patent Document 1: K. D. Durst and H. Kronmuller, “THE COERCIVE     FIELD OF SINTERED AND MELT-SPUN NdFeB MAGNETS,” Journal of Magnetism     and Magnetic Materials, 68 (1987), 63-75 -   Non-Patent Document 2: K. T. Park, K. Hiraga and M. Sagawa, “Effect     of Metal-Coating and Consecutive Heat Treatment on Coercivity of     Thin Nd—Fe—B Sintered Magnets,” Proceedings of the Sixteen     International Workshop on Rare-Earth Magnets and Their Applications,     Sendai, p. 257 (2000) -   Non-Patent Document 3: K. Machida, et al., “Grain Boundary     Modification of Nd—Fe—B Sintered Magnet and Magnetic Properties,”     Proceedings of 2004 Spring Meeting of the Powder & Powder Metallurgy     Society, p. 202

SUMMARY OF INVENTION

An object of the invention is to provide an R—Fe—B sintered magnet which is prepared by coating a sintered magnet body with a powder mixture of an intermetallic compound, alloy or metal powder and a rare earth oxide and effecting diffusion treatment and which magnet features efficient productivity, excellent magnetic performance, a minimal amount of Tb or Dy used, an increased coercive force, and a minimized decline of remanence. Another object is to provide a method for preparing the same.

Regarding the surface coating of an R—Fe—B sintered body with a rare earth oxide which is the best from the aspect of productivity, the inventors attempted to increase the diffusion amount. The inventors have discovered that when a mixture of an oxide containing a rare earth element such as Dy or Tb and an intermetallic compound or metal powder is used for coating, a significant amount of Dy or Tb can be introduced near interfaces of primary phase grains within the magnet through the passages in the form of grain boundaries, as compared with the method of effecting heat treatment after coating with a rare earth inorganic compound powder such as fluoride or oxide, because the oxide is partially reduced during heat treatment. As a consequence, the coercive force of the magnet is increased while minimizing a decline of remanence. Additionally, the process is improved in productivity over the prior art processes. The invention is predicated on this discovery.

The invention provides rare earth permanent magnets and methods for preparing the same, as defined below.

[1] A method for preparing a rare earth permanent magnet, comprising the steps of:

disposing a powder mixture on a surface of a sintered magnet body having the composition R_(a)T¹ _(b)M_(c)B_(d) wherein R is at least one element selected from rare earth elements inclusive of Y and Sc, T¹ is one or both of Fe and Co, M is at least one element selected from the group consisting of Al, Si, C, P, Ti, V, Cr, Mn, Ni, Cu, Zn, Ga, Ge, Zr, Nb, Mo, Ag, In, Sn, Sb, Hf, Ta, W, Pb, and Bi, B is boron, “a,” “b,” “c” and “d” indicative of atomic percent are in the range: 12≤a≤20, 0≤c≤10, 4.0≤d≤7.0, the balance of b, and a+b+c+d=100, the powder mixture comprising an alloy powder having the composition R¹ _(i)M¹ _(j) wherein R¹ is at least one element selected from rare earth elements inclusive of Y and Sc, M¹ is at least one element selected from the group consisting of Al, Si, C, P, Ti, V, Cr, Mn, Ni, Fe, Co, Cu, Zn, Ga, Ge, Zr, Nb, Mo, Ag, In, Sn, Sb, Hf, Ta, W, Pb, and Bi, “i” and “j” indicative of atomic percent are in the range: 15<j≤99, the balance of i, and i+j=100, containing at least 70% by volume of an intermetallic compound phase, and having an average particle size of up to 500 μm, and at least 10% by weight of an R² oxide wherein R² is at least one element selected from rare earth elements inclusive of Y and Sc, having an average particle size of up to 100 μm, and

heat treating the sintered magnet body having the powder mixture disposed on its surface at a temperature lower than or equal to the sintering temperature of the sintered magnet body in vacuum or in an inert gas, for causing the elements R¹, R² and M¹ in the powder mixture to diffuse to grain boundaries in the interior of the sintered magnet body and/or near grain boundaries within the sintered magnet body primary phase grains.

[2] A method for preparing a rare earth permanent magnet, comprising the steps of:

disposing a powder mixture on a surface of a sintered magnet body having the composition R_(a)T¹ _(b)M_(c)B_(d) wherein R is at least one element selected from rare earth elements inclusive of Y and Sc, T¹ is one or both of Fe and Co, M is at least one element selected from the group consisting of Al, Si, C, P, Ti, V, Cr, Mn, Ni, Cu, Zn, Ga, Ge, Zr, Nb, Mo, Ag, In, Sn, Sb, Hf, Ta, W, Pb, and Bi, B is boron, “a,” “b,” “c” and “d” indicative of atomic percent are in the range: 12≤a≤20, 0≤c≤10, 4.0≤d≤7.0, the balance of b, and a+b+c+d=100, the powder mixture comprising an alloy powder having the composition R¹ _(i)M¹ _(j)H_(k) wherein R¹ is at least one element selected from rare earth elements inclusive of Y and Sc, M¹ is at least one element selected from the group consisting of Al, Si, C, P, Ti, V, Cr, Mn, Ni, Fe, Co, Cu, Zn, Ga, Ge, Zr, Nb, Mo, Ag, In, Sn, Sb, Hf, Ta, W, Pb, and Bi, H is hydrogen, “i,” “j” and “k” indicative of atomic percent are in the range: 15<j≤99, 0<k≤(i×2.5), the balance of i, and i+j+k=100, containing at least 70% by volume of an intermetallic compound phase, and having an average particle size of up to 500 μm, and at least 10% by weight of an R² oxide wherein R² is at least one element selected from rare earth elements inclusive of Y and Sc, having an average particle size of up to 100 μm, and

heat treating the sintered magnet body having the powder mixture disposed on its surface at a temperature lower than or equal to the sintering temperature of the sintered magnet body in vacuum or in an inert gas, for causing the elements R¹, R², and M¹ in the powder mixture to diffuse to grain boundaries in the interior of the sintered magnet body and/or near grain boundaries within the sintered magnet body primary phase grains.

[3] The method of [1] or [2] wherein the heat treating step includes heat treatment at a temperature from 200° C. to (Ts−10)° C. for 1 minute to 30 hours wherein Ts represents the sintering temperature of the sintered magnet body. [4] The method of any one of [1] to [3] wherein the disposing step includes dispersing the powder mixture in an organic solvent or water, immersing the sintered magnet body in the resulting slurry, taking up the sintered magnet body, and drying for thereby covering the surface of the sintered magnet body with the powder mixture. [5] A method for preparing a rare earth permanent magnet, comprising the steps of:

disposing a powder mixture on a surface of a sintered magnet body having the composition R_(a)T¹ _(b)M_(c)B_(d) wherein R is at least one element selected from rare earth elements inclusive of Y and Sc, T¹ is one or both of Fe and Co, M is at least one element selected from the group consisting of Al, Si, C, P, Ti, V, Cr, Mn, Ni, Cu, Zn, Ga, Ge, Zr, Nb, Mo, Ag, In, Sn, Sb, Hf, Ta, W, Pb, and Bi, B is boron, “a,” “b,” “c” and “d” indicative of atomic percent are in the range: 12≤a≤20, 0≤c≤10, 4.0≤d≤7.0, the balance of b, and a+b+c+d=100, the powder mixture comprising an alloy powder having the composition R¹ _(x)T² _(y)M¹ _(z) wherein R¹ is at least one element selected from rare earth elements inclusive of Y and Sc, T² is one or both of Fe and Co, M¹ is at least one element selected from the group consisting of Al, Si, C, P, Ti, V, Cr, Mn, Ni, Cu, Zn, Ga, Ge, Zr, Nb, Mo, Ag, In, Sn, Sb, Hf, Ta, W, Pb, and Bi, x, y and z indicative of atomic percent are in the range: 5≤x≤85, 15<z≤95, x+z<100, the balance of y, y>0, and x+y+z=100, containing at least 70% by volume of an intermetallic compound phase, and having an average particle size of up to 500 μm, and at least 10% by weight of an R² oxide wherein R² is at least one element selected from rare earth elements inclusive of Y and Sc, having an average particle size of up to 100 μm, and

heat treating the sintered magnet body having the powder mixture disposed on its surface at a temperature lower than or equal to the sintering temperature of the sintered magnet body in vacuum or in an inert gas, for causing the elements R¹, R², M and T² in the powder mixture to diffuse to grain boundaries in the interior of the sintered magnet body and/or near grain boundaries within the sintered magnet body primary phase grains.

[6] The method of [5] wherein the heat treating step includes heat treatment at a temperature from 200° C. to (Ts−10)° C. for 1 minute to 30 hours wherein Ts represents the sintering temperature of the sintered magnet body. [7] The method of [5] or [6] wherein the disposing step includes dispersing the powder mixture in an organic solvent or water, immersing the sintered magnet body in the resulting slurry, taking up the sintered magnet body, and drying for thereby covering the surface of the sintered magnet body with the powder mixture. [8] The method of any one of [1] to [7] wherein the sintered magnet body has a shape including a minimum portion with a dimension equal to or less than 20 mm. [9] A rare earth permanent magnet, which is prepared by disposing a powder mixture on a surface of a sintered magnet body having the composition R_(a)T¹ _(b)M_(c)B_(d) wherein R is at least one element selected from rare earth elements inclusive of Y and Sc, T¹ is one or both of Fe and Co, M is at least one element selected from the group consisting of Al, Si, C, P, Ti, V, Cr, Mn, Ni, Cu, Zn, Ga, Ge, Zr, Nb, Mo, Ag, In, Sn, Sb, Hf, Ta, W, Pb, and Bi, B is boron, “a,” “b,” “c” and “d” indicative of atomic percent are in the range: 12≤a≤20, 0≤c≤10, 4.0≤d≤7.0, the balance of b, and a+b+c+d=100, the powder mixture comprising an alloy powder having the composition R¹ _(i)M¹ _(j) wherein R¹ is at least one element selected from rare earth elements inclusive of Y and Sc, M¹ is at least one element selected from the group consisting of Al, Si, C, P, Ti, V, Cr, Mn, Ni, Fe, Co, Cu, Zn, Ga, Ge, Zr, Nb, Mo, Ag, In, Sn, Sb, Hf, Ta, W, Pb, and Bi, “i” and “j” indicative of atomic percent are in the range: 15<j≤99, the balance of i, and i+j=100, containing at least 70% by volume of an intermetallic compound phase, and having an average particle size of up to 500 μm, and at least 10% by weight of an R² oxide wherein R² is at least one element selected from rare earth elements inclusive of Y and Sc, having an average particle size of up to 100 μm, and heat treating the sintered magnet body having the powder mixture disposed on its surface at a temperature lower than or equal to the sintering temperature of the sintered magnet body in vacuum or in an inert gas, wherein

the elements R¹, R² and M¹ in the powder mixture are diffused to grain boundaries in the interior of the sintered magnet body and/or near grain boundaries within the sintered magnet body primary phase grains so that the coercive force of the rare earth permanent magnet is increased over the original sintered magnet body.

[10] A rare earth permanent magnet, which is prepared by disposing a powder mixture on a surface of a sintered magnet body having the composition R_(a)T¹ _(b)M_(c)B_(d) wherein R is at least one element selected from rare earth elements inclusive of Y and Sc, T¹ is one or both of Fe and Co, M is at least one element selected from the group consisting of Al, Si, C, P, Ti, V, Cr, Mn, Ni, Cu, Zn, Ga, Ge, Zr, Nb, Mo, Ag, In, Sn, Sb, Hf, Ta, W, Pb, and Bi, B is boron, “a,” “b,” “c” and “d” indicative of atomic percent are in the range: 12≤a≤20, 0≤c≤10, 4.0≤d≤7.0, the balance of b, and a+b+c+d=100, the powder mixture comprising an alloy powder having the composition R¹ _(i)M¹ _(j)H_(k) wherein R¹ is at least one element selected from rare earth elements inclusive of Y and Sc, M¹ is at least one element selected from the group consisting of Al, Si, C, P, Ti, V, Cr, Mn, Ni, Fe, Co, Cu, Zn, Ga, Ge, Zr, Nb, Mo, Ag, In, Sn, Sb, Hf, Ta, W, Pb, and Bi, H is hydrogen, “i,” “j” and “k” indicative of atomic percent are in the range: 15<j≤99, 0<k≤(i×2.5), the balance of i, and i+j+k=100, containing at least 70% by volume of an intermetallic compound phase, and having an average particle size of up to 500 μm, and at least 10% by weight of an R² oxide wherein R² is at least one element selected from rare earth elements inclusive of Y and Sc, having an average particle size of up to 100 μm, and heat treating the sintered magnet body having the powder mixture disposed on its surface at a temperature lower than or equal to the sintering temperature of the sintered magnet body in vacuum or in an inert gas, wherein

the elements R¹, R² and M¹ in the powder mixture are diffused to grain boundaries in the interior of the sintered magnet body and/or near grain boundaries within the sintered magnet body primary phase grains so that the coercive force of the rare earth permanent magnet is increased over the original sintered magnet body.

[11] A rare earth permanent magnet, which is prepared by disposing a powder mixture on a surface of a sintered magnet body having the composition R_(a)T¹ _(b)M_(c)B_(d) wherein R is at least one element selected from rare earth elements inclusive of Y and Sc, T¹ is one or both of Fe and Co, M is at least one element selected from the group consisting of Al, Si, C, P, Ti, V, Cr, Mn, Ni, Cu, Zn, Ga, Ge, Zr, Nb, Mo, Ag, In, Sn, Sb, Hf, Ta, W, Pb, and Bi, B is boron, “a,” “b,” “c” and “d” indicative of atomic percent are in the range: 12≤a≤20, 0≤c≤10, 4.0≤d≤7.0, the balance of b, and a+b+c+d=100, the powder mixture comprising an alloy powder having the composition R¹ _(x)T² _(y)M¹ _(z) wherein R¹ is at least one element selected from rare earth elements inclusive of Y and Sc, T² is one or both of Fe and Co, M¹ is at least one element selected from the group consisting of Al, Si, C, P, Ti, V, Cr, Mn, Ni, Cu, Zn, Ga, Ge, Zr, Nb, Mo, Ag, In, Sn, Sb, Hf, Ta, W, Pb, and Bi, x, y and z indicative of atomic percent are in the range: 5≤x≤85, 15<z≤95, x+z<100, the balance of y, y>0, and x+y+z=100, containing at least 70% by volume of an intermetallic compound phase, and having an average particle size of up to 500 μm, and at least 10% by weight of an R² oxide wherein R² is at least one element selected from rare earth elements inclusive of Y and Sc, having an average particle size of up to 100 μm, and heat treating the sintered magnet body having the powder mixture disposed on its surface at a temperature lower than or equal to the sintering temperature of the sintered magnet body in vacuum or in an inert gas, wherein

the elements R¹, R², M¹ and T² in the powder mixture are diffused to grain boundaries in the interior of the sintered magnet body and/or near grain boundaries within the sintered magnet body primary phase grains so that the coercive force of the rare earth permanent magnet is increased over the original sintered magnet body.

[12] A method for preparing a rare earth permanent magnet, comprising the steps of:

disposing a powder mixture on a surface of a sintered magnet body having the composition R_(a)T¹ _(b)M_(c)B_(d) wherein R is at least one element selected from rare earth elements inclusive of Y and Sc, T¹ is one or both of Fe and Co, M is at least one element selected from the group consisting of Al, Si, C, P, Ti, V, Cr, Mn, Ni, Cu, Zn, Ga, Ge, Zr, Nb, Mo, Ag, In, Sn, Sb, Hf, Ta, W, Pb, and Bi, B is boron, “a,” “b,” “c” and “d” indicative of atomic percent are in the range: 12≤a≤20, 0≤c≤10, 4.0≤d≤7.0, the balance of b, and a+b+c+d=100, the powder mixture comprising an alloy powder having the composition M¹ _(d)M² _(e) wherein M¹ and M² each are at least one element selected from the group consisting of Al, Si, C, P, Ti, V, Cr, Mn, Ni, Fe, Co, Cu, Zn, Ga, Ge, Zr, Nb, Mo, Ag, In, Sn, Sb, Hf, Ta, W, Pb, and Bi, M¹ and M² are different, “d” and “e” indicative of atomic percent are in the range: 0.1≤e≤99.9, the balance of d, and d+e=100, containing at least 70% by volume of an intermetallic compound phase, and having an average particle size of up to 500 μm, and at least 10% by weight of an R² oxide wherein R² is at least one element selected from rare earth elements inclusive of Y and Sc, having an average particle size of up to 100 μm, and

heat treating the sintered magnet body having the powder mixture disposed on its surface at a temperature lower than or equal to the sintering temperature of the sintered magnet body in vacuum or in an inert gas, for causing the elements R², M¹ and M² in the powder mixture to diffuse to grain boundaries in the interior of the sintered magnet body and/or near grain boundaries within the sintered magnet body primary phase grains.

[13] A method for preparing a rare earth permanent magnet, comprising the steps of:

disposing a powder mixture on a surface of a sintered magnet body having the composition R_(a)T¹ _(b)M_(c)B_(d) wherein R is at least one element selected from rare earth elements inclusive of Y and Sc, T¹ is one or both of Fe and Co, M is at least one element selected from the group consisting of Al, Si, C, P, Ti, V, Cr, Mn, Ni, Cu, Zn, Ga, Ge, Zr, Nb, Mo, Ag, In, Sn, Sb, Hf, Ta, W, Pb, and Bi, B is boron, “a,” “b,” “c” and “d” indicative of atomic percent are in the range: 12≤a≤20, 0≤c≤10, 4.0≤d≤7.0, the balance of b, and a+b+c+d=100, the powder mixture comprising an M¹ powder wherein M¹ is at least one element selected from the group consisting of Al, Si, C, P, Ti, V, Cr, Mn, Ni, Fe, Co, Cu, Zn, Ga, Ge, Zr, Nb, Mo, Ag, In, Sn, Sb, Hf, Ta, W, Pb, and Bi, having an average particle size of up to 500 μm, and at least 10% by weight of an R² oxide wherein R² is at least one element selected from rare earth elements inclusive of Y and Sc, having an average particle size of up to 100 μm, and

heat treating the sintered magnet body having the powder mixture disposed on its surface at a temperature lower than or equal to the sintering temperature of the sintered magnet body in vacuum or in an inert gas, for causing the elements R² and M¹ in the powder mixture to diffuse to grain boundaries in the interior of the sintered magnet body and/or near grain boundaries within the sintered magnet body primary phase grains.

[14] The method of [12] or [13] wherein the heat treating step includes heat treatment at a temperature from 200° C. to (Ts−10)° C. for 1 minute to 30 hours wherein Ts represents the sintering temperature of the sintered magnet body. [15] The method of any one of [12] to [14] wherein the disposing step includes dispersing the powder mixture in an organic solvent or water, immersing the sintered magnet body in the resulting slurry, taking up the sintered magnet body, and drying for thereby covering the surface of the sintered magnet body with the powder mixture. [16] The method of any one of [12] to [15] wherein the sintered magnet body has a shape including a minimum portion with a dimension equal to or less than 20 mm. [17] A rare earth permanent magnet, which is prepared by disposing a powder mixture on a surface of a sintered magnet body having the composition R_(a)T¹ _(b)M_(c)B_(d) wherein R is at least one element selected from rare earth elements inclusive of Y and Sc, T¹ is one or both of Fe and Co, M is at least one element selected from the group consisting of Al, Si, C, P, Ti, V, Cr, Mn, Ni, Cu, Zn, Ga, Ge, Zr, Nb, Mo, Ag, In, Sn, Sb, Hf, Ta, W, Pb, and Bi, B is boron, “a,” “b,” “c” and “d” indicative of atomic percent are in the range: 12≤a≤20, 0≤c≤10, 4.0≤d≤7.0, the balance of b, and a+b+c+d=100, the powder mixture comprising an alloy powder having the composition M¹ _(d)M² _(e) wherein M¹ and M² each are at least one element selected from the group consisting of Al, Si, C, P, Ti, V, Cr, Mn, Ni, Fe, Co, Cu, Zn, Ga, Ge, Zr, Nb, Mo, Ag, In, Sn, Sb, Hf, Ta, W, Pb, and Bi, M¹ and M² are different, “d” and “e” indicative of atomic percent are in the range: 0.1≤e≤99.9, the balance of d, and d+e=100, containing at least 70% by volume of an intermetallic compound phase, and having an average particle size of up to 500 μm, and at least 10% by weight of an R² oxide wherein R² is at least one element selected from rare earth elements inclusive of Y and Sc, having an average particle size of up to 100 μm, and heat treating the sintered magnet body having the powder mixture disposed on its surface at a temperature lower than or equal to the sintering temperature of the sintered magnet body in vacuum or in an inert gas, wherein

the elements R², M¹ and M² in the powder mixture are diffused to grain boundaries in the interior of the sintered magnet body and/or near grain boundaries within the sintered magnet body primary phase grains so that the coercive force of the rare earth permanent magnet is increased over the original sintered magnet body.

[18] A rare earth permanent magnet, which is prepared by disposing a powder mixture on a surface of a sintered magnet body having the composition R_(a)T¹ _(b)M_(c)B_(d) wherein R is at least one element selected from rare earth elements inclusive of Y and Sc, T¹ is one or both of Fe and Co, M is at least one element selected from the group consisting of Al, Si, C, P, Ti, V, Cr, Mn, Ni, Cu, Zn, Ga, Ge, Zr, Nb, Mo, Ag, In, Sn, Sb, Hf, Ta, W, Pb, and Bi, B is boron, “a,” “b,” “c” and “d” indicative of atomic percent are in the range: 12≤a≤20, 0≤c≤10, 4.0≤d≤7.0, the balance of b, and a+b+c+d=100, the powder mixture comprising an M¹ powder wherein M¹ is at least one element selected from the group consisting of Al, Si, C, P, Ti, V, Cr, Mn, Ni, Fe, Co, Cu, Zn, Ga, Ge, Zr, Nb, Mo, Ag, In, Sn, Sb, Hf, Ta, W, Pb, and Bi, having an average particle size of up to 500 μm, and at least 10% by weight of an R² oxide wherein R² is at least one element selected from rare earth elements inclusive of Y and Sc, having an average particle size of up to 100 μm, and heat treating the sintered magnet body having the powder mixture disposed on its surface at a temperature lower than or equal to the sintering temperature of the sintered magnet body in vacuum or in an inert gas, wherein

the elements R² and M¹ in the powder mixture are diffused to grain boundaries in the interior of the sintered magnet body and/or near grain boundaries within the sintered magnet body primary phase grains so that the coercive force of the rare earth permanent magnet is increased over the original sintered magnet body.

Advantageous Effects of Invention

When a mixture of an oxide containing a rare earth element such as Dy or Tb and an intermetallic compound or metal powder is used for coating, the oxide is partially reduced during subsequent heat treatment. Thus a significant amount of the rare earth element such as Dy or Tb can be introduced near interfaces of primary phase grains within the magnet through the passages in the form of grain boundaries, as compared with the method of effecting heat treatment after coating with a rare earth inorganic compound powder such as fluoride or oxide. As a consequence, the coercive force of the magnet is increased while minimizing a decline of remanence. Additionally, the process is improved in productivity over the prior art processes. The R—Fe—B sintered magnet exhibits excellent magnetic performance, an increased coercive force, and a minimal decline of remanence, despite a minimal amount of Tb or Dy used.

DESCRIPTION OF EMBODIMENTS

Briefly stated, an R—Fe—B sintered magnet is prepared according to the invention by applying a powder mixture of an intermetallic compound-based alloy powder and a rare earth oxide or metal powder onto a sintered magnet body and effecting diffusion treatment. The resultant magnet has advantages including excellent magnetic performance and a minimal amount of Tb or Dy used.

The mother material used herein is a sintered magnet body having the composition R_(a)T¹ _(b)M_(c)B_(d), which is sometimes referred to as “mother sintered body.” Herein R is one or more elements selected from rare earth elements inclusive of yttrium (Y) and scandium (Sc), specifically from among Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, and Lu. The rare earth elements inclusive of Sc and Y account for 12 to 20 atomic percent (at %), and preferably 13 to 18 at % of the sintered magnet body, differently stated, 12≤a≤20, preferably 13≤a≤18. Preferably the majority of R is Nd and/or Pr. Specifically Nd and/or Pr accounts for 50 to 100 at %, more preferably 70 to 100 at % of the rare earth elements. T¹ is one or both of iron (Fe) and cobalt (Co). M is one or more elements selected from the group consisting of Al, Si, C, P, Ti, V, Cr, Mn, Ni, Cu, Zn, Ga, Ge, Zr, Nb, Mo, Ag, In, Sn, Sb, Hf, Ta, W, Pb, and Bi and accounts for 0 to 10 at %, and preferably 0 to 5 at % of the sintered magnet body, differently stated, 0≤c≤10, preferably 0≤c·5. B is boron and accounts for 4 to 7 at % of the sintered magnet body (4≤d≤7). Particularly when B is 5 to 6 at % (5≤d≤6), a significant improvement in coercive force is achieved by diffusion treatment. The balance consists of T¹. Preferably T¹ accounts for 60 to 84 at %, more preferably 70 to 82 at % of the sintered magnet body, differently stated, 60≤b≤84, preferably 70≤b≤82. The subscripts “a,” “b,” “c” and “d” indicative of atomic percent meet a+b+c+d=100.

The alloy for the mother sintered magnet body is prepared by melting metal or alloy feeds in vacuum or an inert gas atmosphere, preferably argon atmosphere, and casting the melt into a flat mold or book mold or strip casting. A possible alternative is a so-called two-alloy process involving separately preparing an alloy approximate to the R₂Fe₁₄B compound composition constituting the primary phase of the relevant alloy and a rare earth-rich alloy serving as a liquid phase aid at the sintering temperature, crushing, then weighing and mixing them. Notably, the alloy approximate to the primary phase composition is subjected to homogenizing treatment, if necessary, for the purpose of increasing the amount of the R₂Fe₁₄B compound phase, since primary crystal α-Fe is likely to be left depending on the cooling rate during casting and the alloy composition. The homogenizing treatment is a heat treatment at 700 to 1,200° C. for at least one hour in vacuum or in an Ar atmosphere. Alternatively, the alloy approximate to the primary phase composition may be prepared by the strip casting technique. To the rare earth-rich alloy serving as a liquid phase aid, the melt quenching and strip casting techniques are applicable as well as the above-described casting technique.

The alloy is generally crushed or coarsely ground to a size of 0.05 to 3 mm, especially 0.05 to 1.5 mm. The crushing step uses a Brown mill or hydrogen decrepitation, with the hydrogen decrepitation being preferred for those alloys as strip cast. The coarse powder is then finely divided to an average particle size of 0.2 to 30 μm, especially 0.5 to 20 μm, for example, on a jet mill using high-pressure nitrogen.

The fine powder is compacted on a compression molding machine under a magnetic field. The green compact is then placed in a sintering furnace where it is sintered in vacuum or in an inert gas atmosphere usually at a temperature of 900 to 1,250° C., preferably 1,000 to 1,100° C. The sintered block thus obtained contains 60 to 99% by volume, preferably 80 to 98% by volume of the tetragonal R₂Fe₁₄B compound as the primary phase, with the balance being 0.5 to 20% by volume of a rare earth-rich phase and 0.1 to 10% by volume of at least one compound selected from among rare earth oxides, and carbides, nitrides and hydroxides of incidental impurities, and mixtures or composites thereof.

The resulting sintered magnet block may be machined or worked into a predetermined shape. In the invention, the elements (including R¹, R², M¹, M² and T²) which are to be diffused into the sintered magnet body interior are supplied from the sintered magnet body surface. Thus, if a minimum portion of the sintered magnet body has too large a dimension, the objects of the invention are not achievable. For this reason, the shape includes a minimum portion having a dimension equal to or less than 20 mm, and preferably equal to or less than 10 mm, with the lower limit being equal to or more than 0.1 mm. The sintered body includes a maximum portion whose dimension is not particularly limited, with the maximum portion dimension being desirably equal to or less than 200 mm.

According to the invention, a diffusion powder selected from the following powder mixtures (i) to (iv) is disposed on the sintered magnet body before diffusion treatment is carried out.

-   (i) a powder mixture of an alloy of the composition R¹ _(i)M¹ _(j)     containing at least 70% by volume of a rare earth intermetallic     compound phase and an R² oxide -   (ii) a powder mixture of an alloy of the composition R¹ _(i)M¹     _(j)H_(k) containing at least 70% by volume of a rare earth     intermetallic compound phase and an R² oxide -   (iii) a powder mixture of an alloy of the composition R¹ _(x)T²     _(y)M¹ _(z) containing at least 70% by volume of a rare earth     intermetallic compound phase and an R² oxide -   (iv) a powder mixture of an alloy of the composition M¹ _(d)M² _(e)     containing at least 70% by volume of an intermetallic compound phase     and an R² oxide -   (v) a powder mixture of a metal M¹ and an R² oxide

The alloy which is often referred to as “diffusion alloy” is in powder form having an average particle size of less than or equal to 500 m. The R² oxide wherein R² is one or more elements selected from rare earth elements inclusive of Y and Sc is in powder form having an average particle size of less than or equal to 100 μm. The powder mixture consists of the diffusion alloy and at least 10% by weight of the R² oxide. The powder mixture is disposed on the surface of the sintered magnet body. The sintered magnet body having the powder mixture disposed on its surface is heat treated at a temperature lower than or equal to the sintering temperature of the sintered magnet body in vacuum or in an inert gas, whereby the oxide in admixture with the (rare earth) intermetallic compound is partially reduced. During the heat treatment, the elements R¹, R², M¹, M² and T² in the powder mixture (selected depending on a particular diffusion powder used) can be diffused to grain boundaries in the interior of the sintered magnet body and/or near grain boundaries within the sintered magnet body primary phase grains, in a more amount than achievable by the prior art methods.

Herein R¹ is one or more elements selected from rare earth elements inclusive of Y and Sc. Preferably the majority of R¹ is Nd and/or Pr. Specifically Nd and/or Pr accounts for 1 to 100 at %, more preferably 20 to 100 at % of R¹. M¹ is one or more elements selected from the group consisting of Al, Si, C, P, Ti, V, Cr, Mn, Ni, Cu, Zn, Ga, Ge, Zr, Nb, Mo, Ag, In, Sn, Sb, Hf, Ta, W, Pb, and Bi. T² is Fe and/or Co.

In the alloy R¹ _(i)M¹ _(j), M¹ accounts for 15 to 99 at %, preferably 20 to 90 at %, differently stated, j=15 to 99, preferably j=20 to 90, with the balance of R¹ (meaning i+j=100).

In the alloy R¹ _(i)M¹ _(j)H_(k), M¹ accounts for 15 to 99 at %, preferably 20 to 90 at %, differently stated, j=15 to 99, preferably j=20 to 90. Hydrogen (H) is present in an amount of 0<k≤(i×2.5) at %, preferably at least 0.1 at % (k≤0.1). The balance consists of R¹ (meaning i+j+k=100), and R¹ is preferably present in an amount of 20 to 90 at %, namely i=20 to 90.

In the alloy R¹ _(x)T² _(y)M¹ _(z), M¹ accounts for 15 to 95 at %, preferably 20 to 90 at %, differently stated, z=15 to 90, preferably z=20 to 90. R¹ accounts for 5 to 85 at %, preferably 10 to 80 at %, differently stated, x=5 to 85, preferably x=10 to 80. The sum of M¹ and R² is less than 100 at % (x+z<100), preferably 25 to 99.5 at % (x+y=25 to 99.5). The balance consists of T² which is Fe and/or Co (meaning x+y+z=100), and y>0. Typically T² accounts for 0.5 to 75 at %, preferably 1 to 60 at %, differently stated, y=0.5 to 75, preferably y=1 to 60.

In the alloy M¹ _(d)M² _(e), M¹ and M² are different from each other and each is one or more elements selected from the group consisting of Al, Si, C, P, Ti, V, Cr, Mn, Ni, Fe, Co, Cu, Zn, Ga, Ge, Zr, Nb, Mo, Ag, In, Sn, Sb, Hf, Ta, W, Pb, and Bi. The subscripts d and e indicative of atomic percent are in the range: 0.1≤e≤99.9, preferably 10≤e≤90, and more preferably 20≤e≤80, with the balance of d.

In the M¹ metal powder, M¹ is one or more elements selected from the group consisting of Al, Si, C, P, Ti, V, Cr, Mn, Ni, Fe, Co, Cu, Zn, Ga, Ge, Zr, Nb, Mo, Ag, In, Sn, Sb, Hf, Ta, W, Pb, and Bi.

The diffusion alloy may contain incidental impurities such as nitrogen (N) and oxygen (O), with an acceptable total amount of such impurities being equal to or less than 4 at %, preferably equal to or less than 2 at %, and more preferably equal to or less than 1 at %.

The diffusion alloy containing at least 70% by volume of the intermetallic compound phase may be prepared, like the alloy for the mother sintered magnet body, by melting metal or alloy feeds in vacuum or an inert gas atmosphere, preferably argon atmosphere, and casting the melt into a flat mold or book mold. A high-frequency melting method and a strip casting method may also be employed. The alloy is then crushed or coarsely ground to a size of about 0.05 to 3 mm, especially about 0.05 to 1.5 mm by means of a Brown mill or hydrogen decrepitation. The coarse powder is then finely divided, for example, by a ball mill, vibration mill or jet mill using high-pressure nitrogen. The smaller the powder particle size, the higher becomes the diffusion efficiency. The diffusion alloy containing the intermetallic compound phase, when powdered, preferably has an average particle size equal to or less than 500 μm, more preferably equal to or less than 300 μm, and even more preferably equal to or less than 100 μm. However, if the particle size is too small, then the influence of surface oxidation becomes noticeable, and handling is dangerous. Thus the lower limit of average particle size is preferably equal to or more than 1 μm. As used herein, the “average particle size” may be determined as a weight average diameter D₅₀ (particle diameter at 50% by weight cumulative, or median diameter) using, for example, a particle size distribution measuring instrument relying on laser diffractometry or the like.

The M¹ metal powder may be prepared by crushing or coarsely grinding a metal mass to a size of 0.05 to 3 mm, especially 0.05 to 1.5 mm on a suitable grinding machine such as a jaw crusher or Brown mill. The coarse powder is then finely divided, for example, by a ball mill, vibration mill or jet mill using high-pressure nitrogen. Alternatively, fine division may be achieved by an atomizing method of ejecting a metal melt through small nozzles under high-pressure gas as mist. The M¹ metal powder has an average particle size equal to or less than 500 μm, more preferably equal to or less than 300 μm, and even more preferably equal to or less than 100 μm. However, if the particle size is too small, then the influence of surface oxidation becomes noticeable, and handling is dangerous. Thus the lower limit of average particle size is preferably equal to or more than 1 μm.

The other component of the powder mixture is an R² oxide which may be any of oxides of rare earth elements inclusive of Y and Sc, preferably oxides containing Dy or Tb. The R² oxide powder has an average particle size equal to or less than 100 μm, more preferably equal to or less than 50 μm, and even more preferably equal to or less than 20 μm. The R² oxide is present in an amount of at least 10% by weight, preferably at least 20% by weight, and more preferably at least 30% by weight of the powder mixture. Less than 10% by weight of the R² oxide is too small for the rare earth oxide to exert its mixing effect. The upper limit of the amount of the R² oxide is up to 99% by weight, especially up to 90% by weight.

After the powder mixture of the diffusion alloy powder or M¹ metal powder and the R² oxide powder is disposed on the surface of the mother sintered magnet body, the mother sintered magnet body coated with the powder mixture is heat treated in vacuum or in an atmosphere of an inert gas such as argon (Ar) or helium (He) at a temperature equal to or below the sintering temperature (designated Ts in ° C.) of the sintered magnet body. This heat treatment is referred to as “diffusion treatment.” The diffusion treatment causes the rare earth oxide in admixture with the intermetallic compound to be partially reduced, whereby elements R¹, R², M¹, M² and T² in the powder mixture are diffused to grain boundaries in the interior of the sintered magnet body and/or near grain boundaries within sintered magnet body primary phase grains in more amounts than achievable in the prior art.

The powder mixture of the diffusion alloy powder or M¹ metal powder and the R² oxide powder is disposed on the surface of the mother sintered magnet body, for example, by dispersing the powder mixture in water or an organic solvent to form a slurry, immersing the magnet body in the slurry, taking up the magnet body, and drying the magnet body by hot air drying or in vacuum or in air. Spray coating is also possible. The slurry may contain 1 to 90% by weight, and preferably 5 to 70% by weight of the powder mixture.

The conditions of diffusion treatment vary with the type and composition of the powder mixture (including the type and composition of two components) and are preferably selected such that elements R¹, R², M¹, M² and T² in the diffusion powder are enriched at grain boundaries in the interior of the sintered magnet body and/or near grain boundaries within sintered magnet body primary phase grains. The temperature of diffusion treatment is equal to or below the sintering temperature (designated Ts in ° C.) of the sintered magnet body. If diffusion treatment is effected above Ts, there arise problems that (1) the structure of the sintered magnet body can be altered to degrade magnetic properties, and (2) the machined dimensions cannot be maintained due to thermal deformation. For this reason, the temperature of diffusion treatment is equal to or below Ts° C. of the sintered magnet body, and preferably equal to or below (Ts−10)° C. The lower limit of temperature may be selected as appropriate though the temperature is typically at least 200° C., preferably at least 350° C., and more preferably at least 600° C. The time of diffusion treatment is typically from 1 minute to 30 hours. Within less than 1 minute, the diffusion treatment is not complete. If the treatment time exceeds 30 hours, the structure of the sintered magnet body can be altered, oxidation or evaporation of components inevitably occurs to degrade magnetic properties, or R¹, R², M¹, M² and T² are not only enriched near grain boundaries in the interior of the sintered body and/or grain boundaries within sintered body primary phase grains, but also diffused into the interior of primary phase grains. The preferred time of diffusion treatment is from 1 minute to 10 hours, and more preferably from 10 minutes to 6 hours.

Through appropriate diffusion treatment, the constituent elements R¹, R², M¹, M² and T² in the powder mixture disposed on the surface of the sintered magnet body are diffused into the sintered magnet body while traveling mainly along grain boundaries in the sintered magnet body structure. This results in the structure in which R¹, R², M¹, M² and T² are enriched near grain boundaries in the interior of the sintered magnet body and/or grain boundaries within sintered magnet body primary phase grains.

The permanent magnet thus obtained is improved in coercivity because the diffusion of R¹, R², M¹, M² and T² modifies the morphology near the primary phase grain boundaries within the structure so as to suppress a decline of magnetocrystalline anisotropy at primary phase grain boundaries or to create a new phase at grain boundaries. Since the elements in the powder mixture have not diffused into the interior of primary phase grains, a decline of remanence is restrained. The magnet is a high performance permanent magnet.

After the diffusion treatment, the magnet may be further subjected to aging treatment at a temperature of 200 to 900° C. for augmenting the coercivity enhancement.

EXAMPLE

Examples are given below for further illustrating the invention although the invention is not limited thereto.

Example 1 and Comparative Examples 1 and 2

An alloy was prepared by weighing amounts of Nd, Co, Al and Fe metals having a purity of at least 99% by weight and ferroboron, high-frequency heating in an argon atmosphere for melting, and casting the alloy melt on a single roll of copper in an argon atmosphere, that is, strip casting into a strip of alloy. The alloy consisted of 12.8 at % of Nd, 1.0 at % of Co, 0.5 at % of Al, 6.0 at % of B, and the balance of Fe. This is designated alloy A. Alloy A was then subjected to hydrogen decrepitation by causing the alloy to absorb hydrogen, vacuum evacuating and heating up to 500° C. for desorbing part of hydrogen. In this way, alloy A was pulverized into a coarse powder under 30 mesh.

Another alloy was prepared by weighing amounts of Nd, Dy, Fe, Co, Al and Cu metals having a purity of at least 99% by weight and ferroboron, high-frequency heating in an argon atmosphere for melting, and casting the alloy melt. The alloy consisted of 23 at % of Nd, 12 at % of Dy, 25 at % of Fe, 6 at % of B, 0.5 at % of Al, 2 at % of Cu, and the balance of Co. This is designated alloy B. Alloy B was ground on a Brown mill in a nitrogen atmosphere into a coarse powder under 30 mesh.

Next, 94 wt % of alloy A powder and 6 wt % of alloy B powder were mixed in a nitrogen-purged V-blender for 30 minutes. The powder mixture was finely pulverized on a jet mill using high-pressure nitrogen gas into a fine powder having a mass median particle diameter of 4.1 μm. The fine powder was compacted in a nitrogen atmosphere under a pressure of about 1 ton/cm² while being oriented in a magnetic field of 15 kOe. The green compact was then placed in a sintering furnace where it was sintered in an argon atmosphere at 1,060° C. for 2 hours, obtaining a magnet block of 10 mm×20 mm×15 mm (thick). Using a diamond grinding tool, the magnet block was machined on all the surfaces into a shape having dimensions of 4 mm×4 mm×2 mm (magnetic anisotropy direction). The machined magnet body was washed in sequence with alkaline solution, deionized water, acid solution, and deionized water, and dried, obtaining a mother sintered magnet body which had the composition: Nd_(13.3)Dy_(0.5)Fe_(bal)Co_(2.4)Cu_(0.1)Al_(0.5)B_(6.0).

Tb and Al metals having a purity of at least 99% by weight were used and high-frequency melted in an argon atmosphere to form a diffusion alloy having the composition Tb₃₃Al₆₇ and composed mainly of an intermetallic compound phase TbAl₂. The alloy was finely pulverized on a ball mill using an organic solvent into a fine powder having a mass median particle diameter of 8.6 μm. On electron probe microanalysis (EPMA), the alloy contained 94% by volume of the intermetallic compound phase TbAl₂.

The diffusion alloy Tb₃₃Al₆₇ powder was mixed with terbium oxide (Tb₄O₇) having an average particle size of 1 μm in a weight ratio of 1:1. The powder mixture was combined with deionized water in a weight fraction of 50% to form a slurry, in which the mother sintered magnet body was immersed for 30 seconds under ultrasonic agitation. The magnet body was pulled up and immediately dried with hot air. The magnet body covered with the powder mixture was diffusion treated in an argon atmosphere at 900° C. for 8 hours, aged at 500° C. for 1 hour, and quenched, yielding a magnet of Example 1.

Separately, the diffusion alloy Tb₃₃Al₆₇ powder having a mass median particle diameter of 8.6 μm alone was combined with deionized water in a weight fraction of 50% to form a slurry, in which the magnet body was immersed for 30 seconds under ultrasonic agitation. The magnet body was pulled up and immediately dried with hot air. The magnet body covered with the diffusion alloy powder was diffusion treated in an argon atmosphere at 900° C. for 8 hours, aged at 500° C. for 1 hour, and quenched, yielding a magnet of Comparative Example 1. In the absence of the diffusion powder, only the mother sintered magnet body was similarly heated treated in vacuum at 900° C. for 8 hours, yielding a magnet of Comparative Example 2.

Table 1 summarizes the composition of the mother sintered magnet body, diffusion rare earth alloy and diffusion rare earth oxide, and a mixing ratio (by weight) of the diffusion powder in Example 1 and Comparative Examples 1 and 2. Table 2 shows the temperature (° C.) and time (hr) of diffusion treatment and the magnetic properties of the magnets. It is seen that the magnet of Example 1 has a coercive force (Hcj) which is greater by 90 kAm⁻¹ than that of Comparative Example 1 and a remanence (Br) which is higher by 8 mT than that of Comparative Example 1. The coercive force (Hcj) of the magnet of Example 1 is greater by 1,090 kAm⁻¹ than that of Comparative Example 2 while a decline of remanence (Br) is only 5 mT.

TABLE 1 Diffusion powder mixture Mother sintered Rare earth Rare earth Mixing ratio magnet body alloy oxide (by weight) Example 1 Nd_(13.3)Dy_(0.5)Fe_(bal)Co_(2.4)Cu_(0.1)Al_(0.5)B_(6.0) Tb₃₃Al₆₇ Tb₄O₇ 50:50 Comparative Nd_(13.3)Dy_(0.5)Fe_(bal)Co_(2.4)Cu_(0.1)Al_(0.5)B_(6.0) Tb₃₃Al₆₇ — Tb₃₃Al₆₇ alone Example 1 Comparative Nd_(13.3)Dy_(0.5)Fe_(bal)Co_(2.4)Cu_(0.1)Al_(0.5)B_(6.0) — — — Example 2

TABLE 2 Diffusion treatment Temperature Time Br Hcj (BH)_(max) (° C.) (hr) (T) (kAm⁻¹) (kJ/m³) Example 1 900 8 1.415 2,130 390 Comparative 900 8 1.407 2,040 386 Example 1 Comparative 900 8 1.420 1,040 380 Example 2

Example 2 and Comparative Example 3

As in Example 1, a mother sintered magnet body having the composition: Nd_(13.3)Dy_(0.5)Fe_(bal)Co_(2.4)Cu_(0.1)Al_(0.5)B_(6.0) was prepared.

Tb, Co, Fe and Al metals having a purity of at least 99% by weight were used and high-frequency melted in an argon atmosphere to form a diffusion alloy having the composition Tb₃₅Fe₂₁Co₂₄Al₂₀. The alloy was finely pulverized on a ball mill using an organic solvent into a fine powder having a mass median particle diameter of 8.9 μm. On EPMA analysis, the alloy contained intermetallic compound phases Tb(FeCoAl)₂, Tb₂(FeCoAl) and Tb₂(FeCoAl)₁₇, which summed to 87% by volume.

The diffusion alloy Tb₃₅Fe₂₁Co₂₄Al₂₀ powder was mixed with Tb₄O₇ having an average particle size of 1 μm in a weight ratio of 1:1. The powder mixture was combined with deionized water in a weight fraction of 50% to form a slurry, in which the mother sintered magnet body was immersed for 30 seconds under ultrasonic agitation. The magnet body was pulled up and immediately dried with hot air. The magnet body covered with the powder mixture was diffusion treated in an argon atmosphere at 900° C. for 8 hours, aged at 500° C. for 1 hour, and quenched, yielding a magnet of Example 2.

In the absence of the diffusion powder, only the mother sintered magnet body was similarly heat treated in vacuum at 900° C. for 8 hours, yielding a magnet of Comparative Example 3.

Table 3 summarizes the composition of the mother sintered magnet body, diffusion rare earth alloy and diffusion rare earth oxide, and a mixing ratio (by weight) of the diffusion powder in Example 2 and Comparative Example 3. Table 4 shows the temperature (° C.) and time (hr) of diffusion treatment and the magnetic properties of the magnets. It is seen that the coercive force (Hcj) of the magnet of Example 2 is greater by 1,020 kAm⁻¹ than that of Comparative Example 3 while a decline of remanence (Br) is only 4 mT.

TABLE 3 Diffusion powder mixture Mother sintered Rare earth Rare earth Mixing ratio magnet body alloy oxide (by weight) Example 2 Nd_(13.3)Dy_(0.5)Fe_(bal)Co_(2.4)Cu_(0.1)Al_(0.5)B_(6.0) Tb₃₅Fe₂₁Co₂₄Al₂₀ Tb₄O₇ 50:50 Comparative Nd_(13.3)Dy_(0.5)Fe_(bal)Co_(2.4)Cu_(0.1)Al_(0.5)B_(6.0) — — — Example 3

TABLE 4 Diffusion treatment Temperature Time Br Hcj (BH)_(max) (° C.) (hr) (T) (kAm⁻¹) (kJ/m³) Example 2 900 8 1.416 2,060 390 Comparative 900 8 1.420 1,040 380 Example 3

Examples 3 to 55

As in Example 1, a series of mother sintered magnet bodies were coated with a different powder mixture of diffusion alloy and rare earth oxide and diffusion treated at a selected temperature for a selected time. Table 5 summarizes the composition of the mother sintered magnet body, diffusion rare earth alloy and rare earth oxide, and a mixing ratio (by weight) of the diffusion powder. Table 6 shows the temperature (° C.) and time (hr) of diffusion treatment and the magnetic properties of the resulting magnets. All the diffusion alloys contained at least 70% by volume of intermetallic compounds.

TABLE 5 Diffusion powder mixture Mother sintered Rare earth Rare earth Mixing ratio magnet body alloy oxide (by weight) Example 3 Nd_(15.0)Fe_(bal)Co_(1.0)B_(5.4) Nd₃₅Fe₂₀Co₁₅Al₃₀ Tb₄O₇ 30:70 Example 4 Nd_(15.0)Fe_(bal)Co_(1.0)B_(5.4) Nd₃₅Fe₂₅Co₂₀Si₂₀ Dy₂O₃ 60:40 Example 5 Nd_(15.0)Fe_(bal)Co_(1.0)B_(5.4) Nd₃₃Fe₂₀Co₂₇Al₁₅Si₅ Nd₂O₃ 10:90 Example 6 Nd_(11.0)Dy_(2.0)Tb_(2.0)Fe_(bal)Co_(1.0)B_(5.5) Nd₂₈Pr₅Al₆₇ Pr₂O₃ 90:10 Example 7 Nd_(16.5)Fe_(bal)Co_(1.5)B_(6.2) Y₂₁Mn₇₈Cr₁ Dy₂O₃ 50:50 Example 8 Nd_(13.0)Pr_(2.5)Fe_(bal)Co_(2.8)B_(4.8) La₃₃Cu₆₀Co₄Ni₃ Tb₂O₃ 50:50 Example 9 Nd_(13.0)Pr_(2.5)Fe_(bal)Co_(2.8)B_(4.8) La₅₀Ni₄₉V₁ CeO₂ 70:30 Example 10 Nd_(13.0)Dy_(1.5)Fe_(bal)Co_(1.0)B_(5.9) La₃₃Cu_(66.5)Nb_(0.5) La₂O₃ 30:70 Example 11 Nd_(16.5)Fe_(bal)Co_(3.0)B_(4.7) Ce₂₂Ni₁₄Co₅₈Zn₆ Tb₄O₇ 80:20 Example 12 Nd_(16.5)Fe_(bal)Co_(3.0)B_(4.7) Ce₁₇Ni₈₃ CeO₂ 50:50 Example 13 Nd_(17.3)Fe_(bal)Co_(3.5)B_(6.3) Ce₁₁Zn₈₉ Gd₂O₃ 50:50 Example 14 Nd_(16.0)Dy_(1.5)Fe_(bal)Co_(4.5)B_(5.1) Pr₃₃Ge₆₇ Y₂O₃ 50:50 Example 15 Nd_(12.2)Pr_(2.5)Fe_(bal)Co_(1.0)B_(5.3) Tb₃₃Al₆₀H₇ Dy₂O₃ 50:50 Example 16 Nd_(14.5)Pr_(2.5)Fe_(bal)Co_(3.5)B_(5.6) Pr₃₃Al₆₆Zr₁ Tb₄O₇ 75:25 Example 17 Nd_(13.0)Tb_(1.5)Fe_(bal)B_(5.5) Gd₃₂Mn₃₀Fe₃₁Nb₇ Dy₂O₃ 50:50 Example 18 Nd_(12.0)Fe_(bal)Co_(1.0)B_(4.8) Gd₃₇Mn₄₀Co₂₀Mo₃ Tb₄O₇ 25:75 Example 19 Nd_(13.0)Tb_(1.5)Fe_(bal)B_(5.5) Gd₂₁Mn₇₈Mo₁ Dy₂O₃ 40:60 Example 20 Nd_(12.0)Fe_(bal)Co_(1.0)B_(4.8) Gd₃₃Mn₆₆Ta₁ Tb₄O₇ 50:50 Example 21 Nd_(12.0)Pr_(2.7)Fe_(bal)Co_(2.5)B_(5.2) Tb₂₉Fe₄₅Ni₂₀Ag₆ Yb₂O₃ 50:50 Example 22 Nd_(13.0)Pr_(2.0)Fe_(bal)Co_(2.5)B_(5.2) Tb₅₀Ag₅₀ Tb₄O₇ 60:40 Example 23 Nd_(12.5)Dy_(3.0)Fe_(bal)Co_(0.7)B_(5.9) Tb₅₀In₅₀ Dy₂O₃ 50:50 Example 24 Nd_(12.5)Pr_(2.5)Tb_(0.5)Fe_(bal)Co_(0.5)B_(5.0) Dy₃₁Ni₈Cu₅₅Sn₆ Tb₄O₇ 50:50 Example 25 Nd_(10.0)Pr_(2.5)Dy_(2.5)Fe_(bal)Co_(0.6)B_(5.7) Dy₃₃Cu_(66.5)Hf_(0.5) Pr₂O₃ 50:50 Example 26 Nd_(13.0)Pr_(2.2)Fe_(bal)Co_(1.0)B_(5.3) Dy₃₃Fe₆₇ Dy₂O₃ 50:50 Example 27 Nd_(12.8)Pr_(2.5)Tb_(0.2)Fe_(bal)Co_(1.0)B_(4.5) Er₃₃Mn₃₀Co₃₅Ta₂ Tb₄O₇ 50:50 Example 28 Nd_(13.2)Pr_(2.5)Dy_(0.5)Fe_(bal)Co_(3.0)B_(6.3) Er₂₁Mn_(78.6)W_(0.4) Er₂O₃ 50:50 Example 29 Nd_(12.0)Tb_(3.5)Fe_(bal)Co_(3.5)B_(6.2) Yb₂₄Co₅Ni₆₉Bi₂ Tb₄O₇ 50:50 Example 30 Nd_(13.0)Dy_(3.0)Fe_(bal)Co_(2.0)B_(4.8) Yb₅₀Cu₄₉Ti₁ Pr₂O₃ 50:50 Example 31 Nd_(11.0)Tb_(3.5)Fe_(bal)Co_(3.5)B_(6.2) Yb₂₅Ni_(74.5)Sb_(0.5) Yb₂O₃ 50:50 Example 32 Nd_(15.5)Fe_(bal)Co_(1.0)B_(5.3) Nd₃₃Al₆₇ Tb₄O₇ 90:10 Example 33 Nd_(15.1)Fe_(bal)Co_(1.0)B_(5.4) Nd₅₀Si₅₀ Dy₂O₃ 80:20 Example 34 Nd_(14.8)Fe_(bal)Co_(1.0)B_(5.3) Nd₃₃Al₃₇Si₃₀ Dy₂O₃ 20:80 Example 35 Nd_(11.8)Pr_(3.0)Fe_(bal)Co_(1.0)B_(5.3) Nd₃₄Al₆₁H₅ Tb₄O₇ 50:50 Example 36 Nd_(12.3)Dy_(2.5)Fe_(bal)Co_(3.5)B_(5.4) Nd₂₇Pr₆Al₆₇ Tb₄O₇ 50:50 Example 37 Nd_(15.1)Fe_(bal)Co_(1.0)B_(5.3) Dy₃₃Al₆₇ Dy₂O₃ 75:25 Example 38 Nd_(13.6)Tb_(1.5)Fe_(bal)Co_(3.5)B_(5.2) Dy₃₃Ga₆₇ Tb₄O₇ 50:50 Example 39 Nd_(15.1)Fe_(bal)Co_(1.0)B_(5.3) Tb₃₃Al₆₇ Dy₂O₃ 80:20 Example 40 Nd_(13.5)Pr_(2.0)Dy_(2.0)Fe_(bal)Co_(2.5)B_(5.3) Tb₂₂Mn₇₈ Tb₄O₇ 50:50 Example 41 Nd_(12.5)Pr_(2.5)Fe_(bal)Co_(1.0)B_(5.3) Tb₃₃Co₆₇ Dy₂O₃ 50:50 Example 42 Nd_(19.0)Fe_(bal)Co_(3.0)B_(5.4) Y₁₀Co₁₅Zn₇₅ Y₂O₃ 70:30 Example 43 Nd_(18.0)Fe_(bal)Co_(2.5)B_(6.6) Y₆₈Fe₂In₃₀ Tb₄O₇ 50:50 Example 44 Nd_(18.0)Fe_(bal)Co_(3.0)B_(5.4) Y₁₁Zn₈₉ Dy₂O₃ 80:20 Example 45 Nd_(13.5)Pr_(1.5)Dy_(0.8)Fe_(bal)Co_(2.5)B_(4.5) La₃₂Co₄Cu₆₄ Tb₄O₇ 50:50 Example 46 Nd_(13.5)Pr_(1.5)Dy_(0.8)Fe_(bal)Co_(2.5)B_(4.5) La₃₃Cu₆₇ Pr₂O₃ 50:50 Example 47 Nd_(20.0)Fe_(bal)Co_(5.5)B_(4.1) Ce₂₆Pb₇₄ Tb₄O₇ 40:60 Example 48 Nd_(15.2)Fe_(bal)Co_(1.0)B_(5.3) Ce₅₆Sn₄₄ CeO₂ 50:50 Example 49 Nd_(15.5)Dy_(2.5)Tb_(0.5)Fe_(bal)Co_(2.6)B_(4.4) Pr₃₃Fe₃C₆₄ Dy₂O₃ 50:50 Example 50 Nd_(12.5)Dy_(2.0)Tb_(0.5)Fe_(bal)Co_(3.8)B_(6.2) Pr₅₀P₅₀ Nd₂O₃ 50:50 Example 51 Nd_(12.7)Pr_(2.5)Dy_(0.6)Fe_(bal)Co_(1.4)B_(5.6) Gd₅₂Ni₄₈ Tb₄O₇ 70:30 Example 52 Nd_(13.1)Pr_(1.5)Tb_(0.5)Fe_(bal)Co_(2.8)B_(6.3) Gd₃₇Ga₆₃ Dy₂O₃ 60:40 Example 53 Nd_(15.3)Dy_(0.6)Fe_(bal)Co_(1.0)B_(4.9) Er₃₂Mn₆₇Ta₁ Nd₂O₃ 50:50 Example 54 Nd_(14.5)Pr_(1.0)Dy_(0.5)Fe_(bal)Co_(2.8)B_(4.6) Yb₆₈Pb₃₂ Tb₄O₇ 50:50 Example 55 Nd_(12.0)Pr_(1.5)Dy_(0.5)Fe_(bal)Co_(4.2)B_(5.3) Yb₆₉Sn₂₉Bi₂ Yb₂O₃ 80:20

TABLE 6 Diffusion treatment Temperature Time Br Hcj (BH)max (° C.) (hr or min) (T) (kAm⁻1) (kJ/m³) Example 3 780 8 h 1.404 2,032 385 Example 4 880 8 h 1.419 1,992 390 Example 5 820 6 h 1.416 2,036 389 Example 6 750 5 h 1.411 1,987 388 Example 7 930 10 h 1.343 1,008 343 Example 8 780 5 h 1.367 1,225 354 Example 9 890 7 h 1.388 1,219 363 Example 10 820 8 h 1.432 1,052 396 Example 11 450 12 h 1.348 920 349 Example 12 840 6 h 1.353 940 343 Example 13 400 5 h 1.327 1,052 340 Example 14 830 5 h 1.328 1,890 341 Example 15 820 8 h 1.412 2,130 385 Example 16 850 8 h 1.371 2,048 363 Example 17 960 10 h 1.410 1,785 376 Example 18 940 6 h 1.454 1,620 398 Example 19 920 5 h 1.411 1,615 381 Example 20 860 5 h 1.452 1,748 396 Example 21 920 10 h 1.414 1,672 379 Example 22 920 6 h 1.412 1,910 384 Example 23 940 12 h 1.405 1,955 381 Example 24 870 12 h 1.404 1,930 382 Example 25 860 10 h 1.409 1,870 383 Example 26 850 8 h 1.408 2,060 382 Example 27 1,020 8 h 1.376 1,610 362 Example 28 980 12 h 1.368 1,521 363 Example 29 320 15 min 1.397 1,580 370 Example 30 380 25 min 1.351 1,430 354 Example 31 410 40 min 1.430 1,243 390 Example 32 790 8 h 1.404 2,070 382 Example 33 820 10 h 1.421 2,034 388 Example 34 910 5 h 1.416 2,095 386 Example 35 760 8 h 1.417 2,100 386 Example 36 770 8 h 1.421 2,120 387 Example 37 830 8 h 1.410 2,130 384 Example 38 760 3 h 1.414 2,140 386 Example 39 880 8 h 1.416 2,170 389 Example 40 660 20 h 1.353 1,860 354 Example 41 860 8 h 1.414 2,110 386 Example 42 450 12 h 1.317 1,290 326 Example 43 1,030 2 h 1.286 1,346 309 Example 44 450 8 h 1.332 1,211 334 Example 45 660 14 h 1.350 1,407 347 Example 46 620 12 h 1.347 1,314 344 Example 47 520 10 h 1.203 1,305 276 Example 48 460 14 h 1.361 1,120 350 Example 49 860 30 h 1.278 1,258 312 Example 50 360 40 min 1.412 1,185 368 Example 51 960 2 h 1.390 1,545 366 Example 52 850 30 min 1.415 1,410 382 Example 53 700 10 h 1.373 1,099 355 Example 54 750 12 h 1.351 1,460 346 Example 55 420 10 h 1.448 1,020 396

Example 56 and Comparative Example 4

An alloy was prepared by weighing amounts of Nd, Co, Al and Fe metals having a purity of at least 99% by weight and ferroboron, high-frequency heating in an argon atmosphere for melting, and casting the alloy melt on a single roll of copper in an argon atmosphere, that is, strip casting into a strip of alloy. The alloy consisted of 12.8 at % of Nd, 1.0 at % of Co, 0.5 at % of Al, 6.0 at % of B, and the balance of Fe. This is designated alloy A. Alloy A was then subjected to hydrogen decrepitation by causing the alloy to absorb hydrogen, vacuum evacuating and heating up to 500° C. for desorbing part of hydrogen. In this way, alloy A was pulverized into a coarse powder under 30 mesh.

Another alloy was prepared by weighing amounts of Nd, Dy, Fe, Co, Al and Cu metals having a purity of at least 99% by weight and ferroboron, high-frequency heating in an argon atmosphere for melting, and casting the alloy melt. The alloy consisted of 23 at % of Nd, 12 at % of Dy, 25 at % of Fe, 6 at % of B, 0.5 at % of Al, 2 at % of Cu, and the balance of Co. This is designated alloy B. Alloy B was ground on a Brown mill in a nitrogen atmosphere into a coarse powder under 30 mesh.

Next, 94 wt % of alloy A powder and 6 wt % of alloy B powder were mixed in a nitrogen-purged V-blender for 30 minutes. The powder mixture was finely pulverized on a jet mill using high-pressure nitrogen gas into a fine powder having a mass median particle diameter of 4 μm. The fine powder was compacted in a nitrogen atmosphere under a pressure of about 1 ton/cm² while being oriented in a magnetic field of 15 kOe. The green compact was then placed in a sintering furnace where it was sintered in an argon atmosphere at 1,060° C. for 2 hours, obtaining a magnet block of 10 mm×20 mm×15 mm (thick). Using a diamond grinding tool, the magnet block was machined on all the surfaces into a shape having dimensions of 4 mm×4 mm×2 mm (magnetic anisotropy direction). The machined magnet body was washed in sequence with alkaline solution, deionized water, acid solution, and deionized water, and dried, obtaining a mother sintered magnet body which had the composition: Nd_(13.3)Dy_(0.5)Fe_(bal)Co_(2.4)Cu_(0.1)Al_(0.5)B_(6.0).

Al and Co metals having a purity of at least 99% by weight were used and high-frequency melted in an argon atmosphere to form a diffusion alloy having the composition Al₅₀Co₅₀ and composed mainly of an intermetallic compound phase AlCo. The alloy was finely pulverized on a ball mill using an organic solvent into a fine powder having a mass median particle diameter of 8.9 μm. On EPMA analysis, the alloy contained 94% by volume of the intermetallic compound phase AlCo.

The diffusion alloy Al₅₀Co₅₀ powder was mixed with terbium oxide (Tb₄O₇) having an average particle size of 1 μm in a weight ratio of 1:1. The powder mixture was combined with deionized water in a weight fraction of 50% to form a slurry, in which the mother sintered magnet body was immersed for 30 seconds under ultrasonic agitation. The magnet body was pulled up and immediately dried with hot air. The magnet body covered with the powder mixture was diffusion treated in an argon atmosphere at 900° C. for 8 hours, aged at 500° C. for 1 hour, and quenched, yielding a magnet of Example 56.

Separately, terbium oxide having an average particle size of 1 μm alone was combined with deionized water in a weight fraction of 50% to form a slurry, in which the magnet body was immersed for 30 seconds under ultrasonic agitation. The magnet body was pulled up and immediately dried with hot air. The coated magnet body was diffusion treated in an argon atmosphere at 900° C. for 8 hours, aged at 500° C. for 1 hour, and quenched, yielding a magnet of Comparative Example 4.

Table 7 summarizes the composition of the mother sintered magnet body, diffusion alloy and diffusion rare earth oxide, and a mixing ratio (by weight) of the diffusion powder mixture in Example 56 and Comparative Example 4. Table 8 shows the temperature (° C.) and time (hr) of diffusion treatment and the magnetic properties of the magnets. It is seen that the coercive force (Hcj) of the magnet of Example 56 is greater by 90 kAm⁻¹ than that of Comparative Example 4 while a decline of remanence (Br) is only 3 mT. The coercive force (Hcj) of the magnet of Example 56 is greater by 1,040 kAm⁻¹ than that of previous Comparative Example 2 while a decline of remanence (Br) is only 4 mT.

TABLE 7 Diffusion powder mixture Mother sintered Diffusion Rare earth Mixing ratio magnet body alloy oxide (by weight) Example 56 Nd_(13.3)Dy_(0.5)Fe_(bal)Co_(2.4)Cu_(0.1)Al_(0.5)B_(6.0) Al₅₀Co₅₀ Tb₄O₇ 50:50 Comparative Nd_(13.3)Dy_(0.5)Fe_(bal)Co_(2.4)Cu_(0.1)Al_(0.5)B_(6.0) — Tb₄O₇ Tb₄O₇ alone Example 4 Comparative Nd_(13.3)Dy_(0.5)Fe_(bal)Co_(2.4)Cu_(0.1)Al_(0.5)B_(6.0) — — — Example 2

TABLE 8 Diffusion treatment Temperature Time Br Hcj (BH)_(max) (° C.) (hr) (T) (kAm⁻¹) (kJ/m³) Example 56 900 8 1.416 2,080 390 Comparative 900 8 1.419 1,990 393 Example 4 Comparative 900 8 1.420 1,040 380 Example 2

Example 57 and Comparative Example 5

As in Example 56, a mother sintered magnet body having the composition: Nd_(13.3)DY_(0.5)Fe_(bal) Co_(2.4)CU_(0.1)Al_(0.5)B_(6.0) was prepared.

Ni and Al metals having a purity of at least 99% by weight were used and high-frequency melted in an argon atmosphere to form a diffusion alloy having the composition Ni₂₅Al₇₅ and composed mainly of an intermetallic compound phase NiAl₃. The alloy was finely pulverized on a ball mill using an organic solvent into a fine powder having a mass median particle diameter of 9.3 μm. On EPMA analysis, the alloy contained 94% by volume of the intermetallic compound phase NiAl₃.

The diffusion alloy Ni₂₅Al₇₅ powder was mixed with terbium oxide (Tb₄O₇) having an average particle size of 1 μm in a weight ratio of 1:1. The powder mixture was combined with deionized water in a weight fraction of 50% to form a slurry, in which the mother sintered magnet body was immersed for 30 seconds under ultrasonic agitation. The magnet body was pulled up and immediately dried with hot air. The magnet body covered with the powder mixture was diffusion treated in an argon atmosphere at 900° C. for 8 hours, aged at 500° C. for 1 hour, and quenched, yielding a magnet of Example 57. In the absence of the diffusion powder mixture, the sintered magnet body alone was heat treated in vacuum at 900° C. for 8 hours, yielding a magnet of Comparative Example 5.

Table 9 summarizes the composition of the mother sintered magnet body, diffusion alloy and diffusion rare earth oxide, and a mixing ratio (by weight) of the diffusion powder mixture in Example 57 and Comparative Example 5. Table 10 shows the temperature (° C.) and time (hr) of diffusion treatment and the magnetic properties of the magnets. It is seen that the coercive force (Hcj) of the magnet of Example 57 is greater by 1,010 kAm⁻¹ than that of Comparative Example 5 while a decline of remanence (Br) is only 4 mT.

TABLE 9 Diffusion powder mixture Mother sintered Diffusion Rare earth Mixing ratio magnet body alloy oxide (by weight) Example 57 Nd_(13.3)Dy_(0.5)Fe_(bal)Co_(2.4)Cu_(0.1)Al_(0.5)B_(6.0) Ni₂₅Al₇₅ Tb₄O₇ 50:50 Comparative Nd_(13.3)Dy_(0.5)Fe_(bal)Co_(2.4)Cu_(0.1)Al_(0.5)B_(6.0) — — — Example 5

TABLE 10 Diffusion treatment Temperature Time Br Hcj (BH)_(max) (° C.) (hr) (T) (kAm⁻¹) (kJ/m³) Example 57 900 8 1.416 2,050 390 Comparative 900 8 1.420 1,040 380 Example 5

Examples 58 to 96

As in Example 56, a series of mother sintered magnet bodies were coated with a different powder mixture of diffusion alloy (or metal) and rare earth oxide and diffusion treated at a selected temperature for a selected time. Table 11 summarizes the composition of the mother sintered magnet body, diffusion alloy and rare earth oxide, and a mixing ratio (by weight) of the diffusion powder mixture. Table 12 shows the temperature (° C.) and time (hr) of diffusion treatment and the magnetic properties of the resulting magnets. All the diffusion alloys contained at least 70% by volume of intermetallic compounds.

TABLE 11 Diffusion powder mixture Mother sintered Diffusion Rare earth Mixing ratio magnet body alloy or metal oxide (by weight) Example 58 Nd_(15.0)Fe_(bal)Co_(1.0)B_(5.4) Mn₂₇Al₇₃ Tb₄O₇ 30:70 Example 59 Nd_(12.0)Pr_(3.0)Fe_(bal)Co_(3.0)B_(5.2) Ni₂₅Al₇₅ Dy₂O₃ 90:10 Example 60 Nd_(13.3)Dy_(0.5)Fe_(bal)Co_(2.0)B_(6.0) Al Tb₄O₇ 50:50 Example 61 Nd_(14.3)Dy_(1.2)Fe_(bal)Co_(2.0)B_(5.3) Cr_(12.5)Al_(87.5) Nd₂O₃ 20:80 Example 62 Nd_(13.8)Tb_(0.7)Fe_(bal)Co_(1.0)B_(5.5) Co₃₃Si₆₇ Pr₂O₃ 70:30 Example 63 Nd_(15.8)Fe_(bal)Co_(1.5)B_(5.3) Mn₂₅Al₂₅Cu₅₀ Tb₄O₇ 50:50 Example 64 Nd_(14.4)Dy_(0.8)Tb_(0.3)Fe_(bal)Co_(1.0)B_(5.4) Fe₅₀Si₅₀ CeO₂ 60:40 Example 65 Nd_(18.2)Fe_(bal)Co_(4.0)B_(5.3) Fe_(49.9)C_(0.1)Si₅₀ La₂O₃ 30:70 Example 66 Nd_(13.3)Dy_(0.5)Fe_(bal)Co_(2.0)B_(6.0) Si Tb₄O₇ 50:50 Example 67 Nd_(17.6)Fe_(bal)Co_(3.5)B_(4.2) Cr_(12.5)Al_(87.5) Tb₄O₇ 50:50 Example 68 Nd_(15.6)Fe_(bal)Co_(1.0)B_(6.8) Mn₆₇P₃₃ Dy₂O₃ 50:50 Example 69 Nd_(12.0)Fe_(bal)Co_(2.0)B_(6.0) Ti₅₀Cu₅₀ Gd₂O₃ 50:50 Example 70 Nd_(12.9)Dy_(1.0)Fe_(bal)Co_(2.0)B_(6.0) Cu Dy₂O₃ 50:50 Example 71 Nd_(15.2)Fe_(bal)Co_(1.0)B_(5.5) V₇₅Sn₂₅ Tb₄O₇ 75:25 Example 72 Nd_(14.3)Fe_(bal)B_(6.1) Cr₆₇Ta₃₃ Dy₂O₃ 50:50 Example 73 Nd_(14.8)Fe_(bal)Co_(3.0)B_(5.4) Cu₇₅Sn₂₅ Y₂O₃ 50:50 Example 74 Pr_(15.0)Fe_(bal)Co_(6.5)B_(5.3) Cu₇₀Zn₅Sn₂₅ Er₂O₃ 60:40 Example 75 Nd_(13.8)Dy_(0.8)Fe_(bal)Co_(2.0)B_(6.2) Zn Dy₂O₃ 50:50 Example 76 Nd_(15.8)Pr_(1.5)Fe_(bal)Co_(2.5)B_(5.2) Ga₄₀Zr₆₀ Tb₄O₇ 60:40 Example 77 Nd_(13.5)Dy_(1.0)Fe_(bal)Co_(2.0)B_(6.0) Ga Tb₄O₇ 50:50 Example 78 Nd_(15.2)Fe_(bal)Co_(3.0)B_(5.3) Cr₇₅Ge₂₅ Yb₂O₃ 50:50 Example 79 Nd_(14.0)Dy_(0.8)Fe_(bal)Co_(3.0)B_(6.0) Ge Dy₂O₃ 50:50 Example 80 Nd_(14.6)Pr_(2.0)Dy_(0.8)Fe_(bal)Co_(2.0)B_(5.3) Nb₃₃Si₆₇ Dy₂O₃ 50:50 Example 81 Pr_(13.7)Dy_(1.0)Fe_(bal)Co_(1.0)B_(5.4) Al₇₃Mo₂₇ Pr₂O₃ 40:60 Example 82 Nd_(15.0)Fe_(bal)Co_(1.0)B_(6.4) Ti₅₀Ag₅₀ Nd₂O₃ 60:40 Example 83 Nd_(13.8)Dy_(1.0)Fe_(bal)Co_(1.0)B_(5.8) Ag Tb₄O₇ 50:50 Example 84 Nd_(14.3)Fe_(bal)Co_(1.0)B_(5.3) In₂₅Mn₇₅ Tb₄O₇ 50:50 Example 85 Nd_(13.9)Fe_(bal)B_(5.6) Hf₃₃Cr₆₇ Dy₂O₃ 70:30 Example 86 Nd_(15.2)Fe_(bal)Co_(1.0)B_(5.6) Cr₂₅Fe₅₅W₂₀ Tb₄O₇ 50:50 Example 87 Nd_(15.1)Yb_(0.2)Fe_(bal)Co_(1.0)B_(4.8) Ni₅₀Sb₅₀ Er₂O₃ 50:50 Example 88 Nd_(15.7)Fe_(bal)Co_(5.0)B_(6.9) Ti₈₀Pb₂₀ Tb₄O₇ 60:40 Example 89 Nd_(14.6)Fe_(bal)Co_(1.0)B_(5.3) Mn₂₅Co₅₀Sn₂₅ La₂O₃ 70:30 Example 90 Nd_(14.9)Fe_(bal)Co_(0.7)B_(5.3) Co₆₀Sn₄₀ Tb₄O₇ 50:50 Example 91 Nd_(14.6)Fe_(bal)Co_(1.5)B_(5.5) V₇₅Sn₂₅ Er₂O₃ 30:70 Example 92 Nd_(12.8)Pr_(2.0)Fe_(bal)Co_(3.0)B_(5.6) Sn Tb₄O₇ 50:50 Example 93 Nd_(14.2)Fe_(bal)Co_(0.5)B_(5.6) Cr₂₁Fe₆₂Mo₁₇ Tb₄O₇ 50:50 Example 94 Nd_(15.0)Dy_(0.6)Fe_(bal)Co_(0.1)B_(4.1) Bi₄₀Zr₆₀ Dy₂O₃ 40:60 Example 95 Nd_(15.2)Fe_(bal)Co_(3.5)B_(6.4) Ni₅₀Bi₅₀ Yb₂O₃ 50:50 Example 96 Nd_(12.0)Pr_(3.0)Fe_(bal)Co_(2.0)B_(6.1) Bi Dy₂O₃ 50:50

TABLE 12 Diffusion treatment Temperature Time Br Hcj (BH)_(max) (° C.) (hr or min) (T) (kAm⁻¹) (kJ/m³) Example 58 790 3 h 1.413 2,087 387 Example 59 810 3 h 30 min 1.407 2,187 384 Example 60 850 8 h 1.414 1,980 388 Example 61 760 1 h 1.380 1,928 368 Example 62 820 2 h 30 min 1.423 2,042 394 Example 63 770 5 h 1.394 2,223 373 Example 64 820 4 h 1.402 1,861 383 Example 65 940 12 h 1.298 1,904 328 Example 66 870 8 h 1.415 1,930 389 Example 67 1,060 28 h 1.284 1,713 319 Example 68 380 15 min 1.358 1,512 353 Example 69 680 8 h 1.476 1,498 409 Example 70 820 8 h 1.417 1,820 390 Example 71 940 5 h 1.414 1,816 387 Example 72 1,020 10 h 1.426 1,896 393 Example 73 650 8 h 1.420 1,641 387 Example 74 600 10 h 1.406 1,689 379 Example 75 760 8 h 1.403 1,760 379 Example 76 840 5 h 1.355 1,940 351 Example 77 870 8 h 1.415 1,950 389 Example 78 850 7 h 1.420 1,816 390 Example 79 880 8 h 1.411 1,890 387 Example 80 1,000 10 h 1.358 1,896 355 Example 81 770 1 h 1.417 2,085 386 Example 82 760 4 h 1.404 1,530 380 Example 83 920 8 h 1.413 1,910 386 Example 84 630 13 h 1.446 1,780 401 Example 85 960 7 h 1.433 1,620 394 Example 86 920 15 h 1.413 1,940 385 Example 87 750 6 h 1.381 1,537 363 Example 88 920 5 h 1.369 1,338 355 Example 89 640 6 h 1.424 1,418 391 Example 90 880 40 min 1.414 2,040 383 Example 91 1,020 10 h 1.420 1,450 387 Example 92 730 5 h 1.408 1,820 383 Example 93 880 15 h 1.454 1,800 406 Example 94 510 20 h 1.346 1,430 343 Example 95 360 5 min 1.392 1,211 362 Example 96 420 15 min 1.382 1,510 358

Japanese Patent Application Nos. 2011-102787 and 2011-102789 are incorporated herein by reference.

Although some preferred embodiments have been described, many modifications and variations may be made thereto in light of the above teachings. It is therefore to be understood that the invention may be practiced otherwise than as specifically described without departing from the scope of the appended claims. 

What is claimed is:
 1. A method for preparing a rare earth permanent magnet, comprising the steps of: disposing a powder mixture on a surface of a sintered magnet body having the composition R_(a)T¹ _(b)M_(c)B_(d) wherein R is at least one element selected from rare earth elements inclusive of Y and Sc, T¹ is one or both of Fe and Co, M is at least one element selected from the group consisting of Al, Si, C, P, Ti, V, Cr, Mn, Ni, Cu, Zn, Ga, Ge, Zr, Nb, Mo, Ag, In, Sn, Sb, Hf, Ta, W, Pb, and Bi, B is boron, “a,” “b,” “2c” and “d” indicative of atomic percent are in the range: 12≤a≤20, 0≤c≤10, 4.0≤d≤7.0, the balance of b, and a+b+c+d=100, the powder mixture comprising an alloy powder having the composition R¹ _(i)M¹ _(j)H_(k) wherein R¹ is at least one element selected from rare earth elements inclusive of Y and Sc, M¹ is at least one element selected from the group consisting of Al, Si, C, P, Ti, V, Cr, Mn, Ni, Fe, Co, Cu, Zn, Ga, Ge, Zr, Nb, Mo, Ag, In, Sn, Sb, Hf, Ta, W, Pb, and Bi, H is hydrogen, “i,” “j” and “k” indicative of atomic percent are in the range: 15<j≤99, 0<k≤(i×2.5), the balance of i, and i+j+k=100, containing at least 70% by volume of an intermetallic compound phase, and having an average particle size of up to 500 μm, and at least 10% by weight of an R² oxide wherein R² is at least one element selected from rare earth elements inclusive of Y and Sc, having an average particle size of up to 100 μm, and heat treating the sintered magnet body having the powder mixture disposed on its surface at a temperature lower than or equal to the sintering temperature of the sintered magnet body in vacuum or in an inert gas, for causing the elements R¹, R², and M¹ in the powder mixture to diffuse to grain boundaries in the interior of the sintered magnet body and/or near grain boundaries within the sintered magnet body primary phase grains.
 2. The method of claim 1 wherein the heat treating step includes heat treatment at a temperature from 200° C. to (Ts−10)° C. for 1 minute to 30 hours wherein Ts represents the sintering temperature of the sintered magnet body.
 3. The method of claim 1 wherein the disposing step includes dispersing the powder mixture in an organic solvent or water, immersing the sintered magnet body in the resulting slurry, taking up the sintered magnet body, and drying for thereby covering the surface of the sintered magnet body with the powder mixture.
 4. The method of claim 1 wherein the sintered magnet body has a shape including a minimum portion with a dimension equal to or less than 20 mm.
 5. A rare earth permanent magnet, which is prepared by disposing a powder mixture on a surface of a sintered magnet body having the composition R_(a)T¹ _(b)M_(c)B_(d) wherein R is at least one element selected from rare earth elements inclusive of Y and Sc, T¹ is one or both of Fe and Co, M is at least one element selected from the group consisting of Al, Si, C, P, Ti, V, Cr, Mn, Ni, Cu, Zn, Ga, Ge, Zr, Nb, Mo, Ag, In, Sn, Sb, Hf, Ta, W, Pb, and Bi, B is boron, “a,” “b,” “c” and “d” indicative of atomic percent are in the range: 12≤a≤20, 0≤c≤10, 4.0≤d≤7.0, the balance of b, and a+b+c+d=100, the powder mixture comprising an alloy powder having the composition R¹ _(i)M¹ _(j)H_(k) wherein R¹ is at least one element selected from rare earth elements inclusive of Y and Sc, M¹ is at least one element selected from the group consisting of Al, Si, C, P, Ti, V, Cr, Mn, Ni, Fe, Co, Cu, Zn, Ga, Ge, Zr, Nb, Mo, Ag, In, Sn, Sb, Hf, Ta, W, Pb, and Bi, H is hydrogen, “i,” “j” and “k” indicative of atomic percent are in the range: 15<j≤99, 0<k≤(i×2.5), the balance of i, and i+j+k=100, containing at least 70% by volume of an intermetallic compound phase, and having an average particle size of up to 500 μm, and at least 10% by weight of an R² oxide wherein R² is at least one element selected from rare earth elements inclusive of Y and Sc, having an average particle size of up to 100 μm, and heat treating the sintered magnet body having the powder mixture disposed on its surface at a temperature lower than or equal to the sintering temperature of the sintered magnet body in vacuum or in an inert gas, wherein the elements R¹, R² and M¹ in the powder mixture are diffused to grain boundaries in the interior of the sintered magnet body and/or near grain boundaries within the sintered magnet body primary phase grains so that the coercive force of the rare earth permanent magnet is increased over the original sintered magnet body. 